Method for producing metal carbonitride film or metalloid carbonitride film, metal carbonitride film or metalloid carbonitride film, and apparatus for producing metal carbonitride film or metalloid carbonitride film

ABSTRACT

Provided is a method and apparatus that can form a metal carbonitride film or a metalloid carbonitride film at low temperature. A metal carbonitride film or a metalloid carbonitride film is formed by supplying onto a film formation object a nitrogen source and a metal source or a metalloid source, the nitrogen source containing a guanidine compound represented by the following general formula (1): 
     
       
         
         
             
             
         
       
     
     where a plurality of Rs are the same or different, each represent a hydrogen atom, a linear, branched or cyclic alkyl group of 1 to 5 carbon atoms or a trialkylsilyl group of 1 to 9 carbon atoms, and, depending on circumstances, bond to each other to form a ring.

TECHNICAL FIELD

The present invention relates to a method for producing a metalcarbonitride film or a metalloid carbonitride film using a guanidinecompound, a metal carbonitride film or a metalloid carbonitride film,and an apparatus for producing a metal carbonitride film or a metalloidcarbonitride film.

BACKGROUND ART

Recently, in the field of semiconductors, electronic components, and thelike, much research and development has been done on highlychemical-resistant “metal carbonitride films or carbonitride films inwhich carbon exists in metalloid nitride films”. As methods forproducing a metal carbonitride film or a metalloid carbonitride film,there are known, for example, a method for producing it by combining aninorganic nitrogen gas, such as ammonia, and a hydrocarbon gas, such asacetylene (see Patent Literature 1) and a method in which isopropylamineis used as a source of carbon and nitrogen (carbonitriding agent) (seePatent Literature 2).

CITATION LIST Patent Literature

-   Patent Literature 1: JP-A-2007-189173-   Patent Literature 2: JP-A-2009-283587

SUMMARY OF INVENTION Technical Problem

However, the methods for producing a metal carbonitride film or ametalloid carbonitride film according to Patent Literatures 1 and 2 havea problem that a metal carbonitride film or a metalloid carbonitridefilm has a high film formation temperature.

A principal object of the present invention is to provide a method andapparatus that can form a metal carbonitride film or a metalloidcarbonitride film at low temperature.

Solution to Problem

In a method for producing a metal carbonitride film or a metalloidcarbonitride film according to the present invention, a metalcarbonitride film or a metalloid carbonitride film is formed bysupplying onto a film formation object a nitrogen source and a metalsource or a metalloid source, the nitrogen source containing a guanidinecompound represented by the following general formula (1):

where a plurality of Rs are the same or different, each represent ahydrogen atom, a linear, branched or cyclic alkyl group of 1 to 5 carbonatoms or a trialkylsilyl group of 1 to 9 carbon atoms, and, depending oncircumstances, bond to each other to form a ring.

A metal carbonitride film or a metalloid carbonitride film according tothe present invention is one obtained by the method for producing ametal carbonitride film or a metalloid carbonitride film according tothe present invention.

An apparatus for producing a metal carbonitride film or a metalloidcarbonitride film according to the present invention is an apparatus forproducing a metal carbonitride film or a metalloid carbonitride film foruse in the method for producing a metal carbonitride film or a metalloidcarbonitride film according to the present invention. The apparatus forproducing a metal carbonitride film or a metalloid carbonitride filmaccording to the present invention includes a reaction chamber, a metalor metalloid source supplying section, and a nitrogen source supplyingsection. The reaction chamber includes a placement section in which afilm formation object is to be placed. The metal or metalloid sourcesupplying section supplies the metal source or the metalloid source intothe reaction chamber. The nitrogen source supplying section supplies thenitrogen source into the reaction chamber.

Advantageous Effects of Invention

According to the present invention, it is possible to provide a methodand apparatus that can form a metal carbonitride film or a metalloidcarbonitride film at low temperature.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic view showing an apparatus for producing a metalcarbonitride film or a metalloid carbonitride film according to oneembodiment of the present invention.

DESCRIPTION OF EMBODIMENTS

In a method for producing a metal carbonitride film or a metalloidcarbonitride film according to this embodiment, a metal carbonitridefilm or a metalloid carbonitride film is formed by supplying onto a filmformation object a nitrogen source and a metal source or a metalloidsource, the nitrogen source containing a guanidine compound representedby the following general formula (1):

where a plurality of Rs are the same or different, each represent ahydrogen atom, a linear, branched or cyclic alkyl group of 1 to 5 carbonatoms or a trialkylsilyl group of 1 to 9 carbon atoms, and, depending oncircumstances, bond to each other to form a ring. Specifically, as shownin FIG. 1, a film 26 is formed by supplying, to a film formation object23 placed on a placement section 22 provided in a reaction chamber 21 ofan apparatus 20 for producing a metal carbonitride film or a metalloidcarbonitride film, a metal or metalloid source 24 a and a nitrogensource 25 a from a metal or metalloid source supplying section 24 and anitrogen source supplying section 25, respectively, provided in thereaction chamber 21. No particular limitation is placed on the methodfor producing a metal carbonitride film or a metalloid carbonitridefilm. A metal carbonitride film or a metalloid carbonitride film can beproduced, for example, by vapor deposition, such as the CVD process(Chemical Vapor Deposition process; hereinafter, referred to as the CVDprocess) or the ALD (Atomic Layer Deposition; hereinafter, referred toas the ALD process).

In the CVD process and the ALD process, a guanidine compound needs to bevaporized in order to form a film on a film formation object. Forexample, only a guanidine compound may be supplied into a vaporizingchamber and vaporized therein or a guanidine compound solution in whicha guanidine compound is diluted in a solvent may be supplied to thevaporizing chamber and vaporized therein.

Examples of the solvent for the guanidine compound solution includealiphatic hydrocarbons, aromatic hydrocarbons, and ethers. Thesesolvents may be used alone or in combinations of some of them.

Specific examples of aliphatic hydrocarbons include, for example,hexane, methylcyclohexane, ethylcyclohexane, and octane.

Specific examples of aromatic hydrocarbons include, for example,toluene.

Specific examples of ethers include, for example, tetrahydrofuran anddibutyl ether.

In vapor-depositing a metal carbonitride film or a metalloidcarbonitride film using a guanidine compound, for example, the internalpressure in the reaction chamber 21 is preferably 1 Pa to 200 kPa andmore preferably 10 Pa to 110 kPa. The film formation temperature ispreferably below 600° C., more preferably below 550° C., and still morepreferably not more than 500° C. The film formation temperature ispreferably not less than 100° C. and more preferably not less than 200°C. The temperature for vaporizing the guanidine compound is preferably0° C. to 180° C. and more preferably 10° C. to 100° C. The content ofgas of the guanidine compound in the amount of gas to be supplied intothe reaction chamber 21 is preferably 0.1% to 99% by volume and morepreferably 0.5% to 95% by volume.

Note that the film formation temperature in the present invention refersto the temperature of the film formation object during film formation.

(Guanidine Compound)

The guanidine compound is represented by the foregoing general formula(1). In the general formula (1), a plurality of Rs are the same ordifferent and each represent a hydrogen atom, a linear, branched orcyclic alkyl group of 1 to 5 carbon atoms or a trialkylsilyl group of 1to 9 carbon atoms.

Examples of the linear, branched or cyclic alkyl group of 1 to 5 carbonatoms include, for example, a methyl group, an ethyl group, an n-propylgroup, an isopropyl group, an n-butyl group, an isobutyl group, at-butyl group, a pentyl group, a cyclopropyl group, a cyclobutyl group,and a cyclopentyl group.

Examples of the trialkylsilyl group of 1 to 9 carbon atoms include, forexample, a trimethylsilyl group, a triethylsilyl group, adimethylethylsilyl group, and a methyldiethylsilyl group.

The plurality of Rs may bond to each other to form a ring and examplesof the ring to be formed include, for example, saturated or unsaturatedrings of 2 to 10 carbon atoms.

Specific examples of the guanidine compound that is preferably usedinclude, for example, guanidine compounds represented by Formulae (2) to(29) below. These guanidine compounds may be used alone or incombinations of two or more of them.

(Metal Source or Metalloid Source)

The metal source or metalloid source that is preferably used is, forexample, a metal halide or a metalloid halide.

Examples of the metal halide include trichloroaluminum,tribromoaluminum, trifluoroaluminum, triiodoaluminum,tetrabromotitanium, tetrachlorotitanium, tetrafluorotitanium,tetraiodotitanium, tetrabromozirconium, tetrachlorozirconium,tetrafluorozirconium, tetraiodozirconium, tetrabromohafnium,tetrachlorohafnium, tetrafluorohafnium, tetraiodohafnium,pentachlorotantalum, pentachloromolybdenum, hexafluoromolybdenum,bis(cyclopentadienyl)dichloromolybdenum, hexachlorotungsten,hexafluorotungsten, dibromocobalt, dichlorocobalt, difluorocobalt,diiodocobalt, dibromonickel, dichloronickel, diiodonickel,dibromomanganese, dichloromanganese, difluoromanganese, diiodomanganese,monobromocopper, dibromocopper, monochlorocopper, dichlorocopper,difluorocopper, diiodocopper, tribromogallium, trichlorogallium,trifluorogallium, triiodogallium, tribromobismuth, trichlorobismuth,trifluorobismuth, triiodobismuth, tribromoruthenium, trichlororuthenium,trifluororuthenium, trichlororhodium, dibromoplatinum, dichloroplatinum,tetrachloroplatinum, diiodoplatinum, dibromopalladium,dichloropalladium, diiodopalladium, triiodoruthenium,benzenedichlororuthenium, dibromozinc, dichlorozinc, difluorozinc, anddiiodozinc.

Examples of the metalloid halide include tetrachlorosilane,tetrafluorosilane, hexachlorodisilane, chloropentamethyldisilane,dichlorotetramethyldisilane, monochlorosilane, dichlorosilane,trichlorosilane, tetrabromogermanium, tetrachlorogermanium,tetraiodogermanium, tribromoboron, trichloroboron, trifluoroboron, andtriiodoboron.

The method for producing a metal carbonitride film or a metalloidcarbonitride film according to the present invention is suitableparticularly for producing a silicon carbonitride film.

EXAMPLES

Next, the present invention will be described in concrete terms withreference to examples but the scope of the present invention is notlimited to these examples.

Examples 1 to 3 Vapor Deposition Test; Production of SiliconCarbonitride Films

Each film was formed on a 20 mm×20 mm substrate by the CVD process usingthe guanidine compound shown in Table 1 under the conditions shown inTable 1. Furthermore, the formed film was analyzed by XPS (X-rayPhotoelectron Spectroscopy) to identify the film.

TABLE 1 Characteristics of Silicon Film Formation ConditionsCarbonitride Film Example 1 Guanidine compound: (9) Film thickness: 300nm Vaporization temperature of guanidine compound: 30° C. XPS analysis;silicon carbonitride Flow rate of Ar carrier for guanidine compound:film 5 ml/min. Silicon source; hexachlorodisilane Vaporizationtemperature of hexachlorodisilane: 30° C. Flow rate of Ar carrier forhexachlorodisilane: 5 ml/min. Substrate material: SiO₂/Si Substratetemperature: 500° C. Internal pressure in reaction system: 3990 Pa Vapordeposition time; 60 min. Example 2 Guanidine compound: (9) Filmthickness: 100 nm Vaporization temperature of guanidine compound: 30° C.XPS analysis; silicon carbonitride Flow rate of Ar carrier for guanidinecompound: film 5 ml/min. Silicon source; hexachlorodisilane Vaporizationtemperature of hexachlorodisilane: 30° C. Flow rate of Ar carrier forhexachlorodisilane: 5 ml/min. Substrate material: SiO₂/Si Substratetemperature: 350° C. Internal pressure in reaction system: 3990 Pa Vapordeposition time; 60 min. Example 3 Guanidine compound: (9) Filmthickness: 30 nm Vaporization temperature of guanidine compound: 30° C.XPS analysis; silicon carbonitride Flow rate of Ar carrier for guanidinecompound: film 5 ml/min. Silicon source: hexachlorodisilane Vaporizationtemperature of hexachlorodisilane: 30° C. Flow rate of Ar carrier forhexachlorodisilane: 5 ml/min. Substrate material: SiO₂/Si Substratetemperature: 250° C. Internal pressure in reaction system: 3990 Pa Vapordeposition time; 60 min.

It can be seen from the above results that with the use of a guanidinecompound, a silicon carbonitride film can be produced at lowtemperature.

REFERENCE SIGNS LIST

-   20 apparatus for producing a metal carbonitride film or a metalloid    carbonitride film-   21 reaction chamber-   22 placement section-   23 film formation object-   24 metal or metalloid source supplying section-   24 a metal or metalloid source-   25 nitrogen source supplying section-   25 a nitrogen source-   26 film

1. A method for producing a metal carbonitride film or a metalloidcarbonitride film, the method comprising forming a metal carbonitridefilm or a metalloid carbonitride film by supplying onto a film formationobject a nitrogen source and a metal source or a metalloid source, thenitrogen source containing a guanidine compound represented by thefollowing general formula (1):

where a plurality of Rs are the same or different, each represent ahydrogen atom, a linear, branched or cyclic alkyl group of 1 to 5 carbonatoms or a trialkylsilyl group of 1 to 9 carbon atoms, and, depending oncircumstances, bond to each other to form a ring.
 2. The method forproducing a metal carbonitride film or a metalloid carbonitride filmaccording to claim 1, wherein a silicon carbonitride film is formed asthe metalloid carbonitride film.
 3. The method for producing a metalcarbonitride film or a metalloid carbonitride film according to claim 1,wherein a guanidine compound solution containing at least one solventselected from the group consisting of aliphatic hydrocarbons, aromatichydrocarbons, and ethers is used as the nitrogen source.
 4. The methodfor producing a metal carbonitride film or a metalloid carbonitride filmaccording to claim 1, wherein a metal halide or a metalloid halide isused as the metal source or the metalloid source.
 5. The method forproducing a metal carbonitride film or a metalloid carbonitride filmaccording to claim 1, wherein a film formation temperature for the metalcarbonitride film or the metalloid carbonitride film is below 600° C. 6.The method for producing a metal carbonitride film or a metalloidcarbonitride film according to claim 5, wherein the film formationtemperature for the metal carbonitride film or the metalloidcarbonitride film is below 550° C.
 7. The method for producing a metalcarbonitride film or a metalloid carbonitride film according to claim 6,wherein the film formation temperature for the metal carbonitride filmor the metalloid carbonitride film is not more than 500° C.
 8. A metalcarbonitride film or metalloid carbonitride film obtained by the methodfor producing a metal carbonitride film or a metalloid carbonitride filmaccording to claim
 1. 9. An apparatus for producing a metal carbonitridefilm or a metalloid carbonitride film, the apparatus being for use inthe method for producing a metal carbonitride film or a metalloidcarbonitride film according to claim 1, the apparatus comprising: areaction chamber including a placement section in which a film formationobject is to be placed; a metal or metalloid source supplying sectionthat supplies the metal source or the metalloid source into the reactionchamber; and a nitrogen source supplying section that supplies thenitrogen source into the reaction chamber.